CN104293350A - Aggregation-induced light-emitting molecule based on tetraphenylethylenes and preparation method and use thereof - Google Patents
Aggregation-induced light-emitting molecule based on tetraphenylethylenes and preparation method and use thereof Download PDFInfo
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- CN104293350A CN104293350A CN201410454986.XA CN201410454986A CN104293350A CN 104293350 A CN104293350 A CN 104293350A CN 201410454986 A CN201410454986 A CN 201410454986A CN 104293350 A CN104293350 A CN 104293350A
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Abstract
The invention discloses an aggregation-induced light-emitting molecule based on tetraphenylethylenes and a preparation method and a use thereof. The aggregation-induced light-emitting molecule based on tetraphenylethylenes has a structure represented by the formula I or II. Through a Suzuki reaction, a pyrene nucleus is modified by applying four tetraphenylethylenes or derivatives thereof to obtain the target product. Pyrene and tetraphenylethylenes are in meta-position connection or methyl is added between pyrene and tetraphenylethylenes, to make a torsion angle between pyrene and tetraphenylethylenes increased, so that the degree of conjugation between pyrene and tetraphenylethylenes is reduced, and a spectrum is subjected to blue shift. The aggregation-induced light-emitting molecule based on tetraphenylethylenes has a good aggregation-induced light-emitting property, moreover, emits blue light, can be used as a blue-light organic light-emitting diode light-emitting layer material, and is simple in preparation.
Description
Technical field
The present invention relates to blue light material, be specifically related to a kind of aggregation-induced emission molecule based on tetraphenyl ethylene and preparation method thereof and the purposes as blue light organic emissive LED lighting layer material.
Background technology
Organic Light Emitting Diode (OLED) invents first the people such as doctor Deng Qingyun by Eastman Kodak of the U.S. in 1987, owing to having, it does not need that backlight, contrast gradient are high, thickness is thin, visual angle is wide, speed of response is fast, can be used for the characteristic of the excellences such as flexibility panel, be considered to the emerging utilisation technology of follow-on plane full-color display.In three primary colors (red, green and blue) luminous organic material, red light material and green light material can meet business-like demand, but efficient, stable blue light material is still very rare, because the high energy gap that has of blue light material is disadvantageous for current carrier to the injection of luminescent layer and transmission.Therefore, the emphasis that efficient, stable blue light material is the research of current luminous organic material how is obtained.On the other hand, due in OLED, luminescent material exists with the form of solid film, and most blue light material also exists the problem of " aggregation inducing cancellation (aggregation-caused quenching, ACQ) " because intermolecular π-π interacts.Although scientists takes many measures to improve ACQ effect, act on all very limited.
Calendar year 2001, this loyal academician seminar Late Cambrian of the Tang of Hong Kong University of Science and Thchnology also reports a class and has the compound of " aggregation-induced emission (Aggregation Induced Emission; AIE) " character, they are not luminous or only send out very weak light in the solution, but can strong fluorescence be sent when they are in state of aggregation, this, for solving ACQ effect, obtains efficient blue light material and provides an effective path.Large quantity research shows, AIE effect dominant mechanism is because Internal Rotations of Molecules is obstructed (RIR)---when solution state, molecular energy dissipates mainly through the rotation of aromatic ring, and when state of aggregation, because Internal Rotations of Molecules is obstructed, energy can only send fluorescence and dissipation energy by radiative transition.In a series of AIE molecules reported, tetraphenyl ethylene (TPE) due to structure simple, luminous efficiency is high and become most widely used construction unit.With regard to single tetraphenyl ethylene, although it can send strong blue light in the solid state, the current efficiency of the OLED of constructing using it as luminescent layer only has 0.45cd/A.Someone is directly connected by tetraphenyl ethylene and the ACQ unit of some classics and obtains many efficient AIE luminescent materials, but its electroluminescent spectrum all due to the increase of conjugate length red shift arrived sky blue light even green range.Therefore, research emphasis and the difficult point that efficient AIE blue light material becomes field for this reason how is designed and synthesized.
Summary of the invention
The object of the invention is to overcome the shortcoming of prior art and deficiency, develop efficient blue light AIE material, a kind of aggregation-induced emission molecule based on tetraphenyl ethylene is provided.The present invention also aims to provide the preparation method of the aggregation-induced emission molecule of described tetraphenyl ethylene and be used as the purposes of blue light organic emissive LED lighting layer material.
Object of the present invention is achieved through the following technical solutions:
Based on an aggregation-induced emission molecule for tetraphenyl ethylene, be Py-4MethylTPE or Py-4mTPE, wherein the structure of Py-4MethylTPE is such as formula shown in I, the structure of Py-4mTPE such as formula shown in II,
The preparation method of the above-mentioned aggregation-induced emission molecule based on tetraphenyl ethylene, comprises the following steps:
(1) under protection gas, in reaction vessel, add compound 1 and compound 2 or compound 3, the tetrakis triphenylphosphine palladium of alkali and catalytic amount, then adds good solvent and deoxidized water, at 70-80 DEG C, be back to abundant reaction.The structure of described compound 1 as shown in formula III, the structure of compound 2 such as formula shown in IV, the structure of compound 3 such as formula shown in V,
(2) cool after completion of the reaction, then extract with good solvent, collect organic phase, then drying is carried out to it, be spin-dried for, obtain the thick product of aggregation-induced emission molecule based on tetraphenyl ethylene.
Protection gas described in step (1) is preferably nitrogen.
Alkali described in step (1) is preferably potassium hydroxide or salt of wormwood.Preferred, the alkali preparing Py-4MethylTPE used is potassium hydroxide, and the alkali preparing Py-4mTPE used is salt of wormwood.
Good solvent described in step (1) is preferably toluene.
Good solvent described in step (2) is preferably trichloromethane.
Preferably, the preparation method of the described aggregation-induced emission molecule based on tetraphenyl ethylene, further comprising the steps of: the thick product of aggregation-induced emission molecule based on tetraphenyl ethylene obtained above is carried out preliminary separation and purification by silica gel chromatography column chromatography, again the product of separation and purification organic solvent (poor solvent of product, the good solvent of impurity) is carried out reprecipitation.Described silica gel chromatography column chromatography eluent used is preferably sherwood oil and trichloromethane (v/v, 1/1).Described organic solvent is the mixing solutions that the poor solvent of product and the good solvent of impurity form, and be preferably the mixing solutions of sherwood oil and methylene dichloride composition, the volume ratio of sherwood oil and methylene dichloride is preferably 1:10.
The above-mentioned aggregation-induced emission molecule based on tetraphenyl ethylene has the purposes as blue light material, particularly as the purposes of blue light organic emissive LED lighting layer material.
A kind of blue light organic emissive LED lighting layer material, comprises the above-mentioned aggregation-induced emission molecule based on tetraphenyl ethylene.
The present invention modifies pyrene core by Suzuki reaction with four tetraphenyl ethylene or derivatives thereofs and obtains target product.The invention has the advantages that:
(1) by pyrene and tetraphenyl ethylene by between position be connected or between pyrene and tetraphenyl ethylene, add methyl the torsion(al)angle between them is increased, thus the conjugated degree reduced between pyrene and tetraphenyl ethylene, make its blue spectral shift, its organic light emitting diode device result shows that the electroluminescent spectrum of this Series Molecules is all in blue region.
(2) the aggregation inducing cancellation unit pyrene of classics is connected with aggregation-induced emission unit tetraphenyl ethylene, the target product finally obtained also has aggregation-induced emission character, and the introducing of pyrene unit contributes to the transmittability increasing current carrier, increase the thermostability of molecule, its organic light emitting diode device result shows that this Series Molecules all has higher efficiency.
(3) compound of the present invention can be used as organic light-emitting diode layer material, and preparation is simple.
Embodiment
Below in conjunction with specific embodiment, further detailed description is done to the present invention.Should be understood that the following examples are only not used in for illustration of the present invention to limit the scope of the invention.
The present invention is based on the aggregation-induced emission molecule of tetraphenyl ethylene, be Py-4MethylTPE or Py-4mTPE, its synthetic route is as follows:
Raw material used in following embodiment can be buied by market, or the synthesis of available methods known in the art obtains.
The synthesis of embodiment 1Py-4MethylTPE
Under nitrogen protection, in Schlenk pipe, add compound 1 (260mg, 0.5mmol) and compound 2 (1.166g, 2.47mmol), potassium hydroxide (560mg, 10mmol) and Pd (PPh
3)
4(0.20g, 0.08mmol), then adds 30mL toluene and 10mL deoxidized water, reflux at 80 DEG C 3 angels its fully react.After completion of the reaction, product is cooled to room temperature, then uses chloroform extraction, collect organic phase, then use anhydrous Na
2sO
4drying, is spin-dried for, and obtains thick product.With sherwood oil and trichloromethane (v/v, 1/1) for eluent, product silica gel chromatography column chromatography is carried out preliminary separation and purification, finally use methylene dichloride and sherwood oil (v/v, 1/10) carry out reprecipitation and obtain white solid (230mg, productive rate 29%), and use
1h NMR and MS characterizes structure, confirms that this white solid is compound Py-4MethylTPE.
1H?NMR(300MHz,CDCl
3δ):7.70(s,2H),7.60(s,4H),7.16-7.13(m,64H),7.03(s,4H),7.00-6.99(d,4H),1.85-1.90(t,12H)；MS(MALDI?TOF),m/z:1579.7138([M]+,calcd?for?C
124H
90,1578.7043)。
The synthesis of embodiment 2Py-4mTPE
Under nitrogen protection, in Schlenk pipe, add compound 1 (260mg, 0.5mmol) and compound 3 (940mg, 2.05mmol), salt of wormwood (1.38g, 10mmol) and Pd (PPh
3)
4(0.20g, 8%mmol), then adds 30mL toluene and 10mL deoxidized water, reflux at 80 DEG C 3 angels its fully react.After completion of the reaction, product is cooled to room temperature, then uses chloroform extraction, collect organic phase, then use anhydrous Na
2sO
4drying, is spin-dried for, and obtains thick product.With sherwood oil and trichloromethane (v/v, 1/1) be eluent, product silica gel chromatography column chromatography is carried out preliminary separation and purification, finally used methylene dichloride and sherwood oil (v/v, 1/10) carry out reprecipitation and obtain yellow solid (350mg, productive rate 46%), and use
1h NMR,
13c NMR, MS and EA characterize structure, confirm that this yellow solid is compound Py-4mTPE.
1H?NMR(300MHz,CDCl3,δ):7.47(s,4H),7.38(s,2H),7.35(s,2H),7.31(m,8H),7.10-7.14(m,54H),7.05-7.06(m,12H).
13C(300MHz,CDCl
3,δ):143.8,143.8,143.7,143.6,141.4,140.9,140.5,136.6,133.8,131.5,131.4,131.3,130.1,130.0,127.9,127.7,127.7,127.6,126.6,126.5,125.0；MS(MALDI?TOF),m/z:1523.6763([M]+,calcd?for?C120H82,1522.6417)；Anal.Calcd?for?C
120H
82:C,94.58；H,5.42.Found:C,94.24；H,5.637。
Py-4MethylTPE and Py-4mTPE prepared by above-described embodiment is used as the emitting layer material of blue light organic emissive diode.The device current efficiency recorded using Py-4MethylTPE and Py-4mTPE as emitting layer material is respectively 5.14cd/A, and (the CIE chromaticity coordinates of its correspondence is (0.19,0.27)) and 4.02cd/A (the CIE chromaticity coordinates of its correspondence is (0.18,0.16)).
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1., based on an aggregation-induced emission molecule for tetraphenyl ethylene, it is characterized in that structure is such as formula shown in I or formula II:
2. the preparation method of the aggregation-induced emission molecule based on tetraphenyl ethylene according to claim 1, is characterized in that comprising the following steps:
(1) under protection gas shielded, in reaction vessel, add compound 1 and compound 2 or compound 3, the tetrakis triphenylphosphine palladium of alkali and catalytic amount, then adds good solvent and deoxidized water, is back to sufficient reacting in 70-80 DEG C; The structure of described compound 1,2,3 is respectively as shown in formula III, IV, V:
(2) after completion of the reaction, with good solvent extraction after product cooling, collect organic phase, drying obtains the thick product of aggregation-induced emission molecule based on tetraphenyl ethylene.
3. the preparation method of the aggregation-induced emission molecule based on tetraphenyl ethylene according to claim 2, is characterized in that: the protection gas described in step (1) is nitrogen; Described alkali is potassium hydroxide or salt of wormwood; Described good solvent is toluene.
4. the preparation method of the aggregation-induced emission molecule based on tetraphenyl ethylene according to claim 3, is characterized in that: the alkali used of compound shown in preparation formula I is potassium hydroxide, and the alkali used of compound shown in preparation formula II is salt of wormwood.
5. the preparation method of the aggregation-induced emission molecule based on tetraphenyl ethylene according to claim 2, is characterized in that: the good solvent described in step (2) is trichloromethane.
6. the preparation method of the aggregation-induced emission molecule based on tetraphenyl ethylene according to any one of claim 2-5, characterized by further comprising following steps: the thick product of aggregation-induced emission molecule based on tetraphenyl ethylene obtained is carried out preliminary separation and purification by silica gel chromatography column chromatography, then the mixing solutions of the good solvent of the poor solvent of the product product of separation and purification and impurity composition is carried out reprecipitation.
7. the preparation method of the aggregation-induced emission molecule based on tetraphenyl ethylene according to claim 6, is characterized in that: described silica gel chromatography column chromatography eluent used is the sherwood oil of volume ratio 1:1 and the mixing solutions of trichloromethane composition; The mixing solutions of the poor solvent of described product and the good solvent composition of impurity is the sherwood oil of volume ratio 10:1 and the mixing solutions of methylene dichloride composition.
8. the aggregation-induced emission molecule based on tetraphenyl ethylene according to claim 1 is as the purposes of blue light material.
9. the aggregation-induced emission molecule based on tetraphenyl ethylene according to claim 1 is as the purposes of blue light organic emissive LED lighting layer material.
10. a blue light organic emissive LED lighting layer material, is characterized in that: comprise the aggregation-induced emission molecule based on tetraphenyl ethylene according to claim 1.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107141190A (en) * | 2017-06-12 | 2017-09-08 | 宁波大学 | A kind of gathering induced luminescence material and preparation method thereof |
| CN107383094A (en) * | 2017-09-04 | 2017-11-24 | 中山大学 | A kind of novel chiral gathering induced luminescence material and its preparation method and application |
| CN108947766A (en) * | 2018-08-10 | 2018-12-07 | 济南大学 | A kind of fluorine-containing tetraphenylethylene compound and its preparation method and application |
| CN109988099A (en) * | 2019-04-24 | 2019-07-09 | 武汉华星光电半导体显示技术有限公司 | Electroluminescent material, the preparation method of electroluminescent material and luminescent device |
| CN110511179A (en) * | 2019-08-06 | 2019-11-29 | 武汉华星光电半导体显示技术有限公司 | Blue fluorescent material and its production method, electroluminescent device |
| CN114409587A (en) * | 2022-01-26 | 2022-04-29 | 清华大学 | Method for producing AIE molecules, AIE molecules and use thereof |
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| CN103396285A (en) * | 2013-08-19 | 2013-11-20 | 武汉大学 | Compound containing tetraphenyl ethylene unit, preparation method and applications thereof |
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2014
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| US20120037896A1 (en) * | 2009-04-09 | 2012-02-16 | Merck Patent Gmbh | Organic electroluminescence device |
| CN103396285A (en) * | 2013-08-19 | 2013-11-20 | 武汉大学 | Compound containing tetraphenyl ethylene unit, preparation method and applications thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107141190A (en) * | 2017-06-12 | 2017-09-08 | 宁波大学 | A kind of gathering induced luminescence material and preparation method thereof |
| CN107383094A (en) * | 2017-09-04 | 2017-11-24 | 中山大学 | A kind of novel chiral gathering induced luminescence material and its preparation method and application |
| CN107383094B (en) * | 2017-09-04 | 2019-07-16 | 中山大学 | A kind of novel chiral gathering induced luminescence material and its preparation method and application |
| CN108947766A (en) * | 2018-08-10 | 2018-12-07 | 济南大学 | A kind of fluorine-containing tetraphenylethylene compound and its preparation method and application |
| CN108947766B (en) * | 2018-08-10 | 2021-02-26 | 济南大学 | Fluorine-containing tetraphenylethylene compound and preparation method and application thereof |
| CN109988099A (en) * | 2019-04-24 | 2019-07-09 | 武汉华星光电半导体显示技术有限公司 | Electroluminescent material, the preparation method of electroluminescent material and luminescent device |
| CN110511179A (en) * | 2019-08-06 | 2019-11-29 | 武汉华星光电半导体显示技术有限公司 | Blue fluorescent material and its production method, electroluminescent device |
| CN114409587A (en) * | 2022-01-26 | 2022-04-29 | 清华大学 | Method for producing AIE molecules, AIE molecules and use thereof |
| CN114409587B (en) * | 2022-01-26 | 2023-09-26 | 清华大学 | Method for producing AIE molecules, AIE molecules and use thereof |
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